skip to main content


Title: Molybdenum-Suboxide Thin Films as Anode Layers in Planar Lithium Microbatteries
In this paper, we investigate the effects of operational conditions on structural, electronic and electrochemical properties on molybdenum suboxides (MoO3-δ) thin films. The films are prepared using pulsed-laser deposition by varying the deposition temperature (Ts), laser fluence (Φ), the partial oxygen pressure (PO2) and annealing temperature (Ta). We find that three classes of samples are obtained with different degrees of stoichiometric deviation without post-treatment: (i) amorphous MoO3-δ (δ < 0.05) (ii) nearly-stoichiometric samples (δ ≈ 0) and (iii) suboxides MoO3-δ (δ > 0.05). The suboxide films 0.05 ≤ δ ≤ 0.25 deposited on Au/Ti/SiO2/flexible-Si substrates with appropriate processing conditions show high electrochemical performance as an anode layer for lithium planar microbatteries. In the realm of simple synthesis, the MoO3-δ film deposited at 450 °C under oxygen pressure of 13 Pa is a mixture of α-MoO3 and Mo8O23 phases (15:85). The electrochemical test of the 0.15MoO3-0.85Mo8O23 film shows a specific capacity of 484 µAh cm−2 µm−1 after 100 cycles of charge-discharge at a constant current of 0.5 A cm−2 in the potential range 3.0-0.05 V.  more » « less
Award ID(s):
1827745
NSF-PAR ID:
10227598
Author(s) / Creator(s):
; ; ; ; ; ; ;
Date Published:
Journal Name:
Electrochem
Volume:
1
Issue:
2
ISSN:
2673-3293
Page Range / eLocation ID:
160 to 187
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Among ABO3 perovskites, SrMoO3 possesses the lowest electrical resistivity in addition to having high optical transparency in the visible spectrum. This unusual combination of material properties allows it to be a potential replacement for indium tin oxide as a transparent electrode. Thus far, its thin film synthesis has been challenging and limited primarily to pulsed laser deposition and sputtering. Here, we report the growth of SrMoO3 thin films by suboxide molecular beam epitaxy. We demonstrate that optically transparent and conductive SrMoO3 films can be grown by supplying elemental strontium via a conventional effusion cell and thermally evaporating MoO3 pellets as a molybdenum source. The direct supply of a molecular oxygen flux to the MoO3 charge was utilized to prevent reduction to lower oxidation states of the charge to ensure congruent evaporation and, thus, a stable MoO3 molecular flux. The optimal growth conditions were found by varying the Sr to MoO3 flux ratio determined from quartz crystal microbalance measurements and monitoring the growth by reflection high-energy electron diffraction. SrMoO3 thin films with 21 nm thickness were confirmed to be optically transparent with transmission between 75 and 91% throughout the visible spectral range and electrically conducting with a room temperature resistivity of 5.0 × 10−5 Ω cm. This realization of this thin film growth method can be further expanded to the growth of other transition metal perovskites in which cations have extremely low vapor pressure and cannot be evaporated in elemental forms.

     
    more » « less
  2. Two-dimensional (2D) materials with robust ferromagnetic behavior have attracted great interest because of their potential applications in next-generation nanoelectronic devices. Aside from graphene and transition metal dichalcogenides, Bi-based layered oxide materials are a group of prospective candidates due to their superior room-temperature multiferroic response. Here, an ultrathin Bi 3 Fe 2 Mn 2 O 10+ δ layered supercell (BFMO322 LS) structure was deposited on an LaAlO 3 (LAO) (001) substrate using pulsed laser deposition. Microstructural analysis suggests that a layered supercell (LS) structure consisting of two-layer-thick Bi–O slabs and two-layer-thick Mn/Fe–O octahedra slabs was formed on top of the pseudo-perovskite interlayer (IL). A robust saturation magnetization value of 129 and 96 emu cm −3 is achieved in a 12.3 nm thick film in the in-plane (IP) and out-of-plane (OP) directions, respectively. The ferromagnetism, dielectric permittivity, and optical bandgap of the ultrathin BFMO films can be effectively tuned by thickness and morphology variation. In addition, the anisotropy of all ultrathin BFMO films switches from OP dominating to IP dominating as the thickness increases. This study demonstrates the ultrathin BFMO film with tunable multifunctionalities as a promising candidate for novel integrated spintronic devices. 
    more » « less
  3. Abstract

    This work characterizes the structural, magnetic, and ferroelectric properties of epitaxial LuFeO3orthoferrite thin films with different Lu/Fe ratios. LuFeO3thin films are grown by pulsed laser deposition on SrTiO3substrates with Lu/Fe ratio ranging from 0.6 to 1.5. LuFeO3is antiferromagnetic with a weak canted moment perpendicular to the film plane. Piezoresponse force microscopy imaging and switching spectroscopy reveal room temperature ferroelectricity in Lu‐rich and Fe‐rich films, whereas the stoichiometric film shows little polarization. Ferroelectricity in Lu‐rich films is present for a range of deposition conditions and crystallographic orientations. Positive‐up‐negative‐down ferroelectric measurements on a Lu‐rich film yield ≈13 µC cm−2of switchable polarization, although the film also shows electrical leakage. The ferroelectric response is attributed to antisite defects analogous to that of Y‐rich YFeO3, yielding multiferroicity via defect engineering in a rare earth orthoferrite.

     
    more » « less
  4. Abstract

    In recent years, the excitation of surface phonon polaritons (SPhPs) in van der Waals materials received wide attention from the nanophotonics community. Alpha-phase Molybdenum trioxide (α-MoO3), a naturally occurring biaxial hyperbolic crystal, emerged as a promising polaritonic material due to its ability to support SPhPs for three orthogonal directions at different wavelength bands (range 10–20μm). Here, we report on the fabrication, structural, morphological, and optical IR characterization of large-area (over 1 cm2size)α-MoO3polycrystalline film deposited on fused silica substrates by pulsed laser deposition. Due to the random grain distribution, the thin film does not display any optical anisotropy at normal incidence. However, the proposed fabrication method allows us to achieve a singleα-phase, preserving the typical strong dispersion related to the phononic response ofα-MoO3flakes. Remarkable spectral properties of interest for IR photonics applications are reported. For instance, a polarization-tunable reflection peak at 1006 cm−1with a dynamic range of ΔR= 0.3 and a resonanceQ-factor as high as 53 is observed at 45° angle of incidence. Additionally, we report the fulfillment of an impedance matching condition with the SiO2substrate leading to a polarization-independent almost perfect absorption condition (R< 0.01) at 972 cm−1which is maintained for a broad angle of incidence. In this framework our findings appear extremely promising for the further development of mid-IR lithography-free, scalable films, for efficient and large-scale sensors, filters, thermal emitters, and label-free biochemical sensing devices operating in the free space, using far-field detection setups.

     
    more » « less
  5. Abstract

    New deposition techniques for amorphous oxide semiconductors compatible with silicon back end of line manufacturing are needed for 3D monolithic integration of thin‐film electronics. Here, three atomic layer deposition (ALD) processes are compared for the fabrication of amorphous zinc tin oxide (ZTO) channels in bottom‐gate, top‐contact n‐channel transistors. As‐deposited ZTO films, made by ALD at 150–200 °C, exhibit semiconducting, enhancement‐mode behavior with electron mobility as high as 13 cm2V−1s−1, due to a low density of oxygen‐related defects. ZTO deposited at 200 °C using a hybrid thermal‐plasma ALD process with an optimal tin composition of 21%, post‐annealed at 400 °C, shows excellent performance with a record high mobility of 22.1 cm2V–1s–1and a subthreshold slope of 0.29 V dec–1. Increasing the deposition temperature and performing post‐deposition anneals at 300–500 °C lead to an increased density of the X‐ray amorphous ZTO film, improving its electrical properties. By optimizing the ZTO active layer thickness and using a high‐kgate insulator (ALD Al2O3), the transistor switching voltage is lowered, enabling electrical compatibility with silicon integrated circuits. This work opens the possibility of monolithic integration of ALD ZTO‐based thin‐film electronics with silicon integrated circuits or onto large‐area flexible substrates.

     
    more » « less